Forrest A. Landis

Simultaneous measurement of polymerization stress and curing kinetics for photo-polymerized composites with high filler contents

OBJECTIVES Photopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. The present study was to demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS). METHODS Our system consisted of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stress generated by lightly-filled to highly-filled composites. The sample configuration allows the tensometer to be coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission mode. RESULTS Using our instrument design, simultaneous measurements of PS and DC are performed, for the first time, on a commercial composite with ≈80% (by mass) silica particle fillers. The in situ NIR spectrometer collects more than 10 spectra per second, allowing for thorough characterization of reaction kinetics. With increased instrument sensitivity coupled with the ability to collect real time reaction kinetics information, we show that the external constraint imposed by the cantilever beam during polymerization could affect the rate of cure and final degree of polymerization. SIGNIFICANCE The present simultaneous measurement technique is expected to provide new insights into kinetics and property relationships for photopolymerized composites with high filler content such as dental restorative composites.

Polymerization stress evolution of a bulk-fill flowable composite under different compliances

OBJECTIVE To use a compliance-variable instrument to simultaneously measure and compare the polymerization stress (PS) evolution, degree of conversion (DC), and exotherm of a bulk-fill flowable composite to a packable composite. METHODS A bulk-fill flowable composite (Filtek Bulk-fill, FBF) and a conventional packable composite (Filtek Z250, Z250) purchased from 3M ESPE were investigated. The composites were studied using a cantilever-beam based instrument equipped with an in situ near infrared (NIR) spectrometer and a microprobe thermocouple. The measurements were carried out under various instrumental compliances (ranging from 0.3327μm/N to 12.3215μm/N) that are comparable to the compliances of clinically prepared tooth cavities. Correlations between the PS and temperature change as well as the DC were interpreted. RESULTS The maximum PS of both composites at 10min after irradiation decreased with the increase in the compliance of the cantilever beam. The FBF composite generated a lower final stress than the Z250 sample under instrumental compliances less than ca. 4μm/N; however, both materials generated statistically similar PS values at higher compliances. The reaction exotherm and the DC of both materials were found to be independent of compliance. The DC of the FBF sample was slightly higher than that of the packable Z250 composite while the peak exotherm of FBF was almost double that of the Z250 composite. For FBF, a characteristic drop in the PS was observed during the early stage of polymerization for all compliances studied which was not observed in the Z250 sample. This drop was shown to relate to the greater exotherm of the less-filled FBF sample relative to the Z250 composite. SIGNIFICANCE While the composites with lower filler content (low viscosity) are generally considered to have lower PS than the conventional packable composites, a bulk-fill flowable composite was shown to produce lower PS under a lower compliance of constraint as would be experienced if the composite was used as the base material in clinical procedures.

Real-time synchronous measurement of curing characteristics and polymerization stress in bone cements with a cantilever-beam based instrument

An instrumentation capable of simultaneously determining degree of conversion (DC), polymerization stress (PS), and polymerization exotherm (PE) in real time was introduced to self-curing bone cements. This comprises the combination of an in situ high-speed near-infrared spectrometer, a cantilever-beam instrument with compliance-variable feature, and a microprobe thermocouple. Two polymethylmethacrylate-based commercial bone cements, containing essentially the same raw materials but differ in their viscosity for orthopedic applications, were used to demonstrate the applicability of the instrumentation. The results show that for both the cements studied the final DC was marginally different, the final PS was different at the low compliance, the peak of the PE was similar, and their polymerization rates were significantly different. Systematic variation of instrumental compliance for testing reveals differences in the characteristics of PS profiles of both the cements. This emphasizes the importance of instrumental compliance in obtaining an accurate understanding of PS evaluation. Finally, the key advantage for the simultaneous measurements is that these polymerization properties can be correlated directly, thus providing higher measurement confidence and enables a more in-depth understanding of the network formation process.

Simultaneous Measurement of Polymerization Stress Evolution, Conversion Kinetics, and Exotherm in Real-Time

Photopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. Herein, we demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS). Our system consists of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stresses. The sample configuration allows the tensometer being coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission. Using our instrument design, simultaneous measurements of PS, DC, and exotherm are performed, for the first time, on a commercial composite with ~80 % (by mass) silica particle fillers. This new system is expected to provide new insights into kinetics and property relationships for photopolymerized composites.

NIST Development of Reference Material Scaffolds for Tissue Engineering

In consultation with ASTM and other stakeholders in Tissue-Engineered Medical Products (TEMPs) industry, the National Institute of Standards and Technology (NIST) initiated a project designed to produce Reference Material scaffolds for tissue engineering. The rationale for Reference Material scaffolds was developed through several NIST/Industry workshops. In brief, Reference Material scaffolds have multiple uses: facilitating the development and the validation of new test methods that measure interactions among various components of a TEMP; comparison with other scaffolds and scaffold materials in terms of cellular responses, biodegradation, and releases of growth factors; and comparisons of responses among various cell lines. The primary customers for Reference Material scaffolds are expected to be the TEMPs industry, academic researchers, regulators, and standards developing organizations. There are many properties of a TEMP that warrant development of multiple Reference Material scaffolds. Currently, NIST is defining a set of Reference Material scaffolds based on geometric descriptors such as permeability, pore volume, pore size distribution, interconnectivity, and tortuosity. In consultation with ASTM, NIST is testing three candidate scaffolds produced by: three dimensional (3-D) printing, stereolithography, and fused deposition modeling (FDM). Scaffolds made by these methods have been obtained from Mayo Clinic (Rochester, MN), Case Western Reserve University (CWRU) (Cleveland, OH), and Osteopore International (Singapore), respectively, for structural characterization. These prototype scaffolds, with well-defined architectures, have been selected to address the following items of interest: 1) establishment of useful functional definitions of porosity content, interconnectivity, and pores; 2) evaluation of testing methods listed in the Standard Guide for the Porosity of Polymeric Scaffolds for Use in Tissue-Engineered Medical Products, which is being drafted by ASTM. Currently, NIST and the Center for Devices and Radiological Health of the Food and Drug Administration, as well as other groups from US and foreign laboratories, are actively carrying out cross-validation test of these prototype scaffolds.